CN1314785C - High alkali cleaning additive - Google Patents

High alkali cleaning additive Download PDF

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Publication number
CN1314785C
CN1314785C CNB021047502A CN02104750A CN1314785C CN 1314785 C CN1314785 C CN 1314785C CN B021047502 A CNB021047502 A CN B021047502A CN 02104750 A CN02104750 A CN 02104750A CN 1314785 C CN1314785 C CN 1314785C
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Prior art keywords
washing agent
quality
agent
tensio
salicylate
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CN1370816A (en
Inventor
S·哈蒙德
A·普里斯
P·司科尼尔
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Infineum International Ltd
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Infineum International Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M159/00—Lubricating compositions characterised by the additive being of unknown or incompletely defined constitution
    • C10M159/12—Reaction products
    • C10M159/20—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products
    • C10M159/22—Reaction mixtures having an excess of neutralising base, e.g. so-called overbasic or highly basic products containing phenol radicals
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07G—COMPOUNDS OF UNKNOWN CONSTITUTION
    • C07G99/00—Subject matter not provided for in other groups of this subclass
    • C07G99/002—Compounds of unknown constitution containing sulfur
    • C07G99/0024—Overbased compounds
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/02—Hydroxy compounds
    • C10M2207/023—Hydroxy compounds having hydroxy groups bound to carbon atoms of six-membered aromatic rings
    • C10M2207/028—Overbased salts thereof
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2207/00—Organic non-macromolecular hydrocarbon compounds containing hydrogen, carbon and oxygen as ingredients in lubricant compositions
    • C10M2207/26—Overbased carboxylic acid salts
    • C10M2207/262—Overbased carboxylic acid salts derived from hydroxy substituted aromatic acids, e.g. salicylates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10M—LUBRICATING COMPOSITIONS; USE OF CHEMICAL SUBSTANCES EITHER ALONE OR AS LUBRICATING INGREDIENTS IN A LUBRICATING COMPOSITION
    • C10M2219/00—Organic non-macromolecular compounds containing sulfur, selenium or tellurium as ingredients in lubricant compositions
    • C10M2219/08—Thiols; Sulfides; Polysulfides; Mercaptals
    • C10M2219/082—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms
    • C10M2219/087—Thiols; Sulfides; Polysulfides; Mercaptals containing sulfur atoms bound to acyclic or cycloaliphatic carbon atoms containing hydroxy groups; Derivatives thereof, e.g. sulfurised phenols
    • C10M2219/089—Overbased salts
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10N—INDEXING SCHEME ASSOCIATED WITH SUBCLASS C10M RELATING TO LUBRICATING COMPOSITIONS
    • C10N2040/00—Specified use or application for which the lubricating composition is intended
    • C10N2040/25—Internal-combustion engines
    • C10N2040/252—Diesel engines
    • C10N2040/253—Small diesel engines

Abstract

Oil overbased salicylate- phenate detergent additives comprise a complex wherein basic material of the detergent is stabilised by both salicylate and phenate surfactants. The mass % of the salicylate, as a percentage of the total surfactant mass, is greater than 50, provided that, when said mass % is less than 60, the TBN: mass % surfactant ratio of the detergent is 10 or less.

Description

The high alkali cleaning agent
Technical field
The present invention relates to be used for the oil soluble high alkaline salicylate-phenates washing agent of lubricating oil composition, or enriched material, described lubricating oil composition for example is compression ignite (diesel engine) marine engine oil composition.
Background technology
Term " peculiar to vessel " is not limited only that those are employed in water transport ship; Should understand as prior art, it also comprises those that are used for that auxiliary power generation uses, and be used to generate electricity promote mainly those of into fixed continental rise engine.
One type marine diesel is the middling speed Otto cycle engine, is called plunger type engine often.The lubricant (or lubricating oil composition) that is used for this class engine is known, and can be described as plunger type engine oil or TPEO ' s.
The producer is designed to marine diesel to use various diesel oil fuels usually, its scope from low-sulfur and low asphalt content the high-quality light fraction fuel to work in-process inferior or heavy fuel oil as " bunker C fuel (Bunker C) " or have residual fuel oil usually than high-sulfur and asphalt content.The lubricant that uses in this class engine is polluted by the bituminous matter component in the fuel often.This cause engine in service serious cleanliness issues (being sometimes referred to as " pitch-dark "), this problem is general especially in the four-stroke plunger type engine, can find the cam case place filth, settling is arranged and sediment deposit is arranged on crankcase wall at piston scraper ring.In addition, lubricant operating system, can not work well as well heater, strainer and whizzer.Described problem is not only in Otto cycle engine; Two stroke crosshead engines also can be affected.
EP-A-0662508 has narrated a kind of mode that overcomes described problem, and it has used a kind of composition, and described composition comprises the salicylate that the phenates enriched material that replaces greater than 300 hydrocarbon as the TBN of washing agent and hydrocarbon replace.Data acknowledgement in embodiment 2, for the combination of described two kinds of washing agents, use salicylate more than the performance of phenates not as good as phenates more than salicylate.
Summary of the invention
The present invention is unexpected to be found, when salicylate and phenates are the complex compound form and exist, has obtained excellent effect in the time using the salicylate of Duoing than phenates.Complex compound provides the excellent simplicity and the advantage of operability.
The complex compound washing agent is known: for example referring to, international publication number WO97/46643,97/46644,97/46645,97/46646 and 97/46647; And EP-A-0750659.But above-mentioned document does not all specifically disclose the salicylate-phenates washing agent of homosalicylic acid salts contg of the present invention.
In first aspect, the present invention is a kind of oil soluble high alkaline salicylate-phenates washing agent, described additive comprises a kind of complex compound, the alkaline matter that it is characterized in that described washing agent comes stabilization by salicylate and two kinds of tensio-active agents of phenates, wherein in tensio-active agent total mass per-cent, described salicylate quality % be at least 50, be preferably greater than 50, condition be when described quality % less than 60 the time, TBN: the ratio of washing agent tensio-active agent quality % is 10 or littler.
In second aspect, the present invention is a kind of lubricating oil composition, and it comprises the mixture of washing agent of oil and more a spot of first aspect present invention of the lubricant viscosity of more amount.
In the third aspect, the present invention is a kind of method of lubricated plunger tpe marine diesel, comprises the lubricating oil composition that second aspect present invention is provided to described engine.
In fourth aspect, the present invention is a kind of combination, and it comprises:
(a) the plunger tpe marine diesel mechanical part that will lubricate; With
(b) lubricating oil composition of second aspect present invention.
In aspect the 5th, the present invention is that the washing agent of first aspect present invention is used for lubricating oil composition, when described composition is used for the plunger tpe marine diesel, and the purposes of the bituminous matter component in the described composition that suspends.
In this manual:
At total quality % of described additive and whole additives of in described composition, existing, for the active ingredient of thinking described additive
" more amount " is meant the 50 quality % that surpass composition;
" more a small amount of " is meant the 50 quality % that are less than composition,
" comprise " or cognate is meant and has described feature, step, integral body or component, exist or additional one or more further feature, step, integral body or component or its combination but do not get rid of;
" TBN " is the total alkali number of measuring by ASTM D2896;
" oil molten " or " oil can disperse " needn't refer to that described additive is solvable with all proportions in oil, solubilized, misciblely maybe can suspend.But described vocabulary be meant really they in oil for example solubilized or stable dispersion to the degree that is enough in the environment that adopts described oil, apply its predetermined effectiveness.Have, as needs, additional other additive also can contain the special additive of higher amount again;
All listed per-cents all in the quality % of active ingredient, that is, are not considered carrier or thinning oil, except as otherwise noted.
The per-cent of the tensio-active agent in the high alkali cleaning agent, and the various tensio-active agents in surfactant system such as the per-cent of phenol, be the per-cent of measuring by the method for the following stated, described method has pointed out also how " the standard TBN " of high alkali cleaning agent measures.
1. the mensuration of the dialysis of high alkali cleaning agent and standard TBN
Use the normal hexane syphonic effect in Soxhlet extractor (150mm height * 75mm internal diameter), to carry out dialysis the liquid high alkali cleaning agent (not containing other lubricating oil additive substantially) of known quantity (A g, about 20g) through a kind of film.Described film should keep all containing metal materials, and the remainder by all samples basically basically.The example that is suitable for film is by Carters Products, Division of Carter Wallace Inc., New York, the natural rubber film that NY 10105 provides with trade name Trojans.Dialysis thing that obtains when dialysis step is finished and resistates evaporate to dryness are removed the volatilizable thing of any remnants then in vacuum chamber (100 ℃ less than 1torr or less than about 130Pa).To be designated as B in the quality of the dried residue of gram.The per-cent (C) of the high alkali cleaning agent material in liquid sample is provided by following formula:
C = B A × 100 %
" the standard TBN " of high alkali cleaning agent (i.e. the TBN that represents in the mode that is independent of dilution dosage) is the TBN that measures with dried residue according to ASTM D2896.
Amos, R. and Albaugh, E.W. at " Chromatography in PetroleumAnalysis (chromatography in the petroleum analysis) ", Altgelt, K.H. and Gouw, T.H. compile, 417 to 422 pages, Marcel Dekker, Inc., New York and Basel, the background information of the osmotic technique that provides in 1979.
2.TBN mensuration: the ratio of the overall % of tensio-active agent
The dried residue of known quantity (Dg, about 10g) is saved described being hydrolyzed by 8.1 to 8.1.2 of ASTM D3712, and difference is to use the hydrochloric acid of 200ml 25% (volume) (proportion 1.18) at least in the 8.1.1 joint.The amount of employed hydrochloric acid should be enough to make high alkali cleaning agent resistates acidifying/be hydrolyzed to organic substance (tensio-active agent) and inorganic substance (calcareous material such as calcium chloride).With the ether extract that merges by it is carried out drying by anhydrous sodium sulphate.Ether with cleaning carries out rinsing to sodium sulfate, and with the ethereal solution evaporate to dryness (under about 110 ℃) that merges to produce the hydrolysed residue thing.Quality in the dry hydrolysed residue thing of gram is designated as E.
The per-cent Y of the total surfactant in the agent of initial liquid high alkali cleaning is given by the following formula:
Y = E D × C
TBN: total surfactant % ratio, X is provided by following formula:
Figure C0210475000072
Be to be noted that and when determining X, use the quality (that is, not being the form that is the salt of other derivative) of the tensio-active agent that is its free form.For for purpose of brevity, X here is commonly referred to as and is " TBN: tensio-active agent % ratio ", and it is the numerical value of the X that marks with this term everywhere at claims and this specification sheets.
3. the determining of various tensio-active agents (with its free form) in surfactant system
Below Xu Shu technology is from by isolating the various tensio-active agents that are hydrolyzation morphology the high alkali cleaning agent deutero-hydrolysis surfactant mixture.As following pointed, the ratio of various tensio-active agents is the ratios of quality that are the various tensio-active agents of hydrolyzation morphology in the hydrolysis surfactant mixture.Thereby when for example containing calcium phenylate/sulfonate/salicylate surfactant system in the high alkali cleaning agent, the ratio of various tensio-active agents is represented with phenol, sulfonic acid and Whitfield's ointment ratio respectively in described surfactant system.
The ratio of various tensio-active agents can be measured by the following method.
Known quantity (Fg, about 1g) placed the top of 450 * 25mm (internal diameter) sintered glass post that is filled with 60-100US order Florisil by the above-mentioned dry hydrolysed residue thing that obtains.Florisil is the Magnesium Silicate q-agent of 8014-97-9 CAS number.Described post carries out wash-out with seven kinds of solvents of the polarity increase of 250ml part, and described seven kinds of solvents are heptane, hexanaphthene, toluene, ether, acetone, methyl alcohol and are the mixture (proportion 0.88) of 50 volume % chloroforms, 44 volume % Virahols and 6 volume % ammonia solutions at last.Collect each cut, evaporate to dryness is weighed the resistates that obtains, and analyzes the amount (G that determines tensio-active agent contained in described cut then 1, G 2, G 3... g) and character.
Analysis to described cut (or hydrolysed residue thing) for example can be undertaken by chromatogram known to a person of ordinary skill in the art, spectrum and/or titration (color indicator or electromotive force) technology.When the high alkali cleaning agent contains sulfosalt surfactant and salicylate tensio-active agent, usually these surfactant waters are separated the sulfonic acid that obtains and salicylate wash-out from described post together.In this case, under other situation of the ratio that why must be determined at the sulfonic acid in the mixture that contains it in office, the ratio of the sulfonic acid in described mixture can be measured by Epton in Trans.Fa r.Soc.April 1948,226 described methods.
In above method, the quality (in gram, being designated as H1) that is the given tensio-active agent of hydrolyzation morphology is determined by the cut that contains it, thereby the ratio of this tensio-active agent is in the surfactant system of original high alkali cleaning agent
H 1 F × 100 %
Various tensio-active agents based on surfactant system (are its free form, promptly, be not to be salt or other derivative form) per-cent (quality meter) can from as initial substance the ratio of tensio-active agent predict, condition is the per-cent for various tensio-active agent initial substances known its " reactive component ".(term " reactive component " is definition in table 1 and 2 the notes 1 in this specification sheets embodiment).Thereby the per-cent of total surfactant in liquid high alkalinity product (being its free form) can be predicted, and can determine TBN: tensio-active agent % ratio.In addition, can predict standard TBN, condition is that the ratio of high alkali cleaning agent material in liquid high alkalinity product (being the ratio of the liquid high alkalinity product of non-oil or non-reacted surfactant materials) is known.
Having found has good dependency between predictor and the numerical value by above-mentioned measurement.
Be to be noted that lubricating oil composition of the present invention comprises can keeping identical or do not keep independent (promptly independently) component of identical chemical property before and after mixing of qualification.
Below feature of the present invention is discussed in more detail:
The high alkali cleaning agent
Washing agent is a kind of additive that piston deposit forms that reduces, and described settling is high temperature varnish shape thing in engine and lacquer deposit thing for example; Described washing agent has in the acid and performance, and can keep the separate solid that is fine in suspension.It is based on metal " soap ", and promptly the metal-salt of acidic organic compound is sometimes referred to as tensio-active agent.
Washing agent comprises the polar head with long hydrophobic tail, and described polar head comprises the metal-salt of described acid.By being reacted, excessive metallic compound such as oxide compound or oxyhydroxide and sour gas such as carbonic acid gas introduce a large amount of metal matrix (metal base), thereby obtain the high alkali cleaning agent, described washing agent comprise as metal matrix (as carbonate) micella outer field in and washing agent.The TBN of high alkali cleaning agent of the present invention can be 200 or bigger, or 250 or bigger, or 300 or bigger, as 300 to 500, preferred 300 to 400.
As stated, described washing agent is wherein alkaline matter by salicylate and the surfactant-stabilized complex compound form of phenates.Complex compound is different with the mixture of independently high alkali cleaning agent, and the example of this class mixture is the mixture of high alkaline salicylate washing agent and high alkalinity phenates washing agent.
According to a specific embodiments of the present invention, described washing agent be by the mixture to Whitfield's ointment and phenol neutralize, the hybrid complex that obtains of high alkalinityization then.
According to another specific embodiments of the present invention, described washing agent be by phenol is neutralized, to the phenates that produces add salicylate, and carry out high alkalinityization subsequently and prepare.
As institute's general description in International Patent Application Publication No. WO9746643/4/5/6 and 7 (more than mentioned), can be by with in the alkaline metal cpds and the mixture of Whitfield's ointment and phenol, parlkalineization prepares this washing agent that is hybrid complex then.
Also can be as general description in EP-A-0750659 (also mentioning) above, carry out carboxylated (carboxylating), sulfuration and the mixture of calcium salicylate and calcium phenylate carried out the washing agent of the present invention that parlkalineization prepares the salicylate/phenates complex compound that is calcium then by Pyrogentisinic Acid's calcium.
Parlkalineization preferably be lower than 100 ℃, more preferably less than 80 ℃, further more preferably less than 60 ℃, further more preferably less than 40 ℃, most preferably be lower than under 35 ℃ the temperature and carry out.
After carry out parlkalineization, described mixture preferably carries out " hot dipping " step, wherein said mixture is remaining on chosen temperature scope (or under chosen temperature) under the condition of not adding any other chemical reagent, described temperature range is generally equal to or is higher than the temperature of carrying out carbonating, this step carry out the time for up to any carry out other procedure of processing before.In the hot dipping process, usually this mixture is stirred.Hot dipping can be at least 30 minutes suitably long-time arbitrarily, and preferably at least 45 minutes, more preferably at least 60 minutes, particularly at least 90 minutes.The common scope of the temperature that hot dipping is carried out is 15 ℃ of reflux temperatures that extremely are lower than reaction mixture just, is preferably 25 ℃ to 60 ℃; Described temperature should make does not remove any material (as solvent) basically from described system in described hot dipping step process.
Preferably, after first carbonation step (with the hot dipping step, as the words of using), also can in described mixture, add the alkaline calcium compound of another consumption, and, advantageously carry out the hot dipping step after the carbonation step in the described second time with described mixture carbonating once more.
The alkaline calcium compound that is used to prepare the high alkali cleaning agent comprises calcium oxide, calcium hydroxide, alcoholization calcium (alkoxides), calcium carboxylates and their mixture.
The mixture that uses high alkalinity reagent to carry out high alkalinityization generally should contain water, and also can contain one or more solvents, auxiliary agent or other material general in the high alkalinity process.The solvent that is suitable for is the benzene (as toluene or dimethylbenzene) that replaces of benzene, alkyl, halogeno-benzene and the lower alcohol of 8 carbon atoms at the most.Preferred solvent is toluene, methyl alcohol and their mixture.Preferred promoter is methyl alcohol, water and their mixture.
Washing agent of the present invention can be basic metal or alkaline-earth metal, as sodium, potassium, lithium, calcium and magnesium washing agent.Preferred calcium.
The tensio-active agent that is used for the surfactant system of high alkalinity metal washing agent can contain at least a alkyl as the substituting group of conduct on aromatic ring.Term used herein " alkyl " is meant that related group mainly is made up of hydrogen and carbon atom, and is connected with the rest part of molecule through carbon atom, but does not get rid of other atom or the group that exists ratio to be not enough to reduce the basic hydrocarbon characteristic of described group.Advantageously, be aliphatic group at the hydrocarbyl group that is used for tensio-active agent of the present invention, preferred alkyl or alkylidene group, particularly alkyl, it is straight or branched.The total number of carbon atoms in described tensio-active agent should be enough to give required oil soluble at least.
But salicylate unvulcanised of the present invention or sulfurized, and chemical modification and/or contain additional substituting group, as following phenates is discussed.Also can be used for the salicylate that alkyl replaces is carried out vulcanizing with following those similar methods, and be that those of ordinary skills are known.Whitfield's ointment usually by phenates by carboxylated, prepare by the Kolbe-Schmitt method, and in this case, generally obtain (usually in thinner) by mixture with not carboxylated phenol.
In the preferred substituents in the salicylate is those that represented by R in the explanation following Pyrogentisinic Acid.In the salicylate that alkyl replaces, described alkyl advantageously contains 5 to 100 carbon atoms, preferred 9 to 30 carbon atoms, particularly 14 to 20 carbon atoms.
Phenates of the present invention is unvulcanized or preferred sulfurized.In addition, described term comprises by containing more than the phenol of a hydroxyl (as alkyl catechol) or thick aromatic ring (as alkyl naphthol) with by the phenol of chemical reaction modification such as the phenol and the Mannich alkali condensation phenol of alkylidene group bridging; With bigcatkin willow alcohols phenol (under alkaline condition react prepare by phenol and aldehyde) institute's deutero-phenates.
Preferred phenates be by the phenol institute deutero-of following general formula those:
Wherein R represents hydrocarbyl group, and y represents 1 to 4.Wherein y is greater than 1, and described alkyl can be identical or different.
The phenol that derives phenates often is the sulfuration form.Sulfuration alkyl phenol can be represented by following general formula usually:
Wherein x is generally 1 to 4.In some cases, can be more than two phenol molecule by S xBridging connects.
In above-mentioned general formula, the hydrocarbyl group of being represented by R is alkyl advantageously, and it advantageously contains 5 to 100 carbon atoms, preferred 5 to 40 carbon atoms, it is about 9 that 9 to 12 carbon atoms particularly, the average carbon atom number in all R groups are at least, to guarantee the suitable solubleness in oil.Preferred alkyl is nonyl (tripropylene) group.
In following discussion, for the phenol that for simplicity hydrocarbon is replaced is called alkylphenol.
The vulcanizing agent that is used to prepare phenol red or phenates can be between the alkylphenol monomeric groups and introduces-(S) xAny compound or the element of-bridged group, wherein x is generally 1 to about 4.Thereby described reaction available element sulphur or its halogenide carry out, described halogenide such as sulfur dichloride or sulfur monochloride more preferably.As use elementary sulfur, can by to alkylphenol compound 50 to 250 ℃, preferably heat under at least 100 ℃ and realize described vulcanization reaction.The aforesaid bridged group of the common generation of use element-(S) x-mixture.As use halogenation sulphur, can by-10 ℃ to 120 ℃, preferably at least 60 ℃ handle described alkylphenols down and realize described vulcanization reaction.Described reaction can be carried out existing under the condition of suitable thinner.Described thinner advantageously comprises basic be inert organic thinner such as mineral oil or paraffinic hydrocarbons.Under any circumstance, described reaction time of carrying out is for being enough to realization response basically.For every normal vulcanizing agent, the preferred usually alkylphenol material that adopts 0.1 to 5 mole.
When using elementary sulfur, advantageously can use alkaline catalysts, for example sodium hydroxide or organic amine, preferably heterocyclic amine (as morpholine) as vulcanizing agent.
The details of vulcanization process is that those of ordinary skills are known.
In a kind of form of the present invention, salicylate-phenates is unvulcanized.
In washing agent of the present invention, when the salicylate quality % in described washing agent is 60 or when bigger, TBN: tensio-active agent quality % ratio is preferably 10 or littler.International publication number WO97/46645 has narrated TBN: how tensio-active agent quality % ratio is measured.
Further preferably, as the salicylate of tensio-active agent total mass per-cent quality % be 65 or bigger, be preferably 70 or bigger, or more preferably 75 or bigger.
The salicylate surfactant content of preferred washing agent is greater than 30, as greater than 35 quality %, and the phenates surfactant content of described washing agent is greater than 8, as 10 or bigger quality %.
Advantageously, the dynamic viscosity of washing agent of the present invention under 100 ℃ is less than 1000mm 2s -1, preferred 50 to 1000mm 2s -1, more preferably 100 to 500mm 2s -1
Lubricating oil composition
For a second aspect of the present invention is provided, described high alkali cleaning agent is joined in the oil (or basic material) of lubricant viscosity in any easy mode.Thereby by under the temperature of room temperature or rising, it is dispersed or dissolved in oil with required concentration, they directly can be added in the described oil, described dispersing or dissolving also can be by means of the solvent such as toluene or the hexanaphthene that are suitable for.
Because washing agent of the present invention has high TBN and high activity substance content simultaneously, so can come the mixed lubrication oil compositions with lower washing agent processing rate, has higher TBN and organic carboxylate surfactant concentration simultaneously.
Preferably, described composition is lubricant peculiar to vessel such as TPEO.Preferably, said composition is the plunger tpe marine engine oil.Said composition optionally has the oil fuel of irreducible oil content.
Lubricating oil composition of the present invention has found to alleviate especially effectively aforesaid " pitch-dark " problem.
The basic raw material that is used for described composition can be synthetic or natural.
Synthetic basic raw material comprises the alkyl ester of dicarboxylic acid, polyglycol and alcohol; Poly-alpha-olefin comprises polybutene; Alkylbenzene; Organophosphate; And polysiloxane oil.
Natural basic raw material is included in the mineral lubricating oils that changes in the wide region, as concerning its primary source, can be alkane, naphthenic, blended or alkane-naphthenic, employed preparation method such as the boiling range, they can be straight run or cracked, hydrorefined or solvent-extracted in its preparation.
Easily, be applicable to that the lubricating oil basic raw material in the crankcase lubricant is 2.5 to 12mm 100 ℃ of following viscosity 2/ s, but also can use the basic raw material of other viscosity, as bright stock (bright stock).
Easily, be applicable to that the lubricating oil basic raw material in the lubricant peculiar to vessel is 3 to 15mm 100 ℃ of following viscosity 2/ s, but also can use the basic raw material of other viscosity.Thereby for example, can use usually 100 ℃ of following viscosity is 30 to 35mm 2The bright stock of/s.
Can in described composition, add additional additives and make it to satisfy specific demand.The example of the additional additives that can comprise in the lubricating oil composition that contains high alkali cleaning agent of the present invention is viscosity index improver, inhibiter; Oxidation inhibitor or antioxidant, friction improver, dispersion agent, other washing agent, metal antirusting agent, anti-wear agent, pour point pour point depressant and defoamer.The lubricating oil that is applicable to ship engine advantageously comprises dispersion agent and anti-wear agent as additional additives, and can contain other additive, as additional antioxidant, defoamer and/or rust-preventive agent.Below more indicated additional additives be used for the ship engine lubricant and compare and be applicable to that more motor car engine with lubricator.
Described composition contains the additive of 5 to the 40 quality % that have an appointment usually, and all the other are base oil.
Embodiment
Embodiment
Following embodiment is illustrated the present invention, but not it is limited.
Salicylate-phenates the washing agent of preparation high alkalinity calcium
In reactor, introduce 637g toluene, 191g methyl alcohol, 33g water and 19g thinning oil (SN150), and remain under about 20 ℃ condition in temperature and to mix.Add calcium hydroxide (Ca (OH) 2) (136g), and under agitation condition with this mixture heating up to 40 ℃.In the soup compound that obtains by this way, add 521g alkyl salicylate and 134g sulfuration nonyl phenol.
The temperature of described mixture is reduced to about 28 ℃, and remaining under the condition of this temperature, injecting carbon dioxide (44g) in 90 to 120 fens described mixtures of clockwise.Through 60 minutes temperature is risen to 60 ℃ then, then this mixture is cooled to about 28 ℃ temperature through 30 minutes.Under 28 ℃, add the calcium hydroxide (88g) of another amount again, temperature is being maintained at about under 28 ℃ the condition then, through 90 to 120 minutes times injecting carbon dioxide (44g) in described mixture again.After this second carbonation step, temperature was brought up to 60 ℃ through 90 minutes.In this heat treated phase process, when temperature reaches 45 ℃, add a collection of thinning oil (41g) in addition.
Synthetic for finishing, product is heated to 160 ℃ by 60 ℃ desolvates and water in about four hours time to remove.This solvent stripping process carries out in three stages:
Under atmospheric pressure,, add final a collection of thinning oil (40g) at this point to 114 ℃;
Under the pressure of 500mba r between 114 ℃ to 125 ℃;
Under the pressure of 250mba r between 125 ℃ to 160 ℃.
At last, filtration product is also diluted with base oil (30g) with disgorging.
The feature of the high alkali cleaning agent that is made by this method is as follows:
TBN=325mgKOH/g (measuring) by ASTM D2896
Kv100=277cSt (measuring) by ASTM D445
Active component content=86 quality % (being calculated as [final product quality-base oil quality]/[final product quality])

Claims (19)

1. oil soluble high alkaline salicylate-phenates washing agent, comprise a kind of complex compound, the alkaline matter that it is characterized in that described washing agent is surfactant-stabilized by salicylate and phenates, per-cent in the tensio-active agent total mass, described salicylate quality % be at least 65, condition is that each component concentration sum of tensio-active agent is 100 quality %.
2. according to the washing agent of claim 1, wherein in the per-cent of tensio-active agent total mass, salicylate quality % be 70 or bigger, condition is that each component concentration sum of tensio-active agent is 100 quality %.
3. according to the washing agent of claim 1, wherein in the per-cent of tensio-active agent total mass, described salicylate quality % be 75 or bigger, condition is that each component concentration sum of tensio-active agent is 100 quality %.
4. according to each washing agent of claim 1 to 3, wherein said washing agent is the alkaline-earth metal washing agent.
5. according to the washing agent of claim 4, wherein said washing agent is calcium or magnesium washing agent.
6. according to the washing agent of claim 1, its TBN that has is 200-500.
7. according to the washing agent of claim 6, its TBN that has is 300-500.
8. according to the washing agent of claim 1, its dynamic viscosity that has under 100 ℃ is 50 to 1000mm 2s -1
9. washing agent according to Claim 8, its dynamic viscosity that has under 100 ℃ are 100 to 500mm 2s -1
10. according to the washing agent of claim 1, the salicylate surfactant content of wherein said washing agent is greater than 30 quality %, the phenates surfactant content of described washing agent is greater than 8 quality %, and condition is that each component concentration sum of tensio-active agent of washing agent is 100 quality %.
11. washing agent according to claim 11, the Whitfield's ointment surfactant content of wherein said washing agent is greater than 35 quality %, the phenates surfactant content of described washing agent is greater than 10 quality %, and condition is that each component concentration sum of tensio-active agent of washing agent is 100 quality %.
12. according to the washing agent of claim 1, wherein said washing agent be by the mixture to Whitfield's ointment and phenol neutralize, the hybrid complex that obtains of high alkalinityization then.
13. according to the washing agent of claim 1, wherein said washing agent be by phenol is neutralized, to the phenates that produces add salicylate, and carry out high alkalinityization subsequently and prepare.
14. a lubricating oil composition, comprise greater than the oil of the lubricant viscosity of 50 quality % with less than 50 quality % according to each the mixture of washing agent of claim 1 to 13, condition is that each component concentration sum of composition is 100 quality %.
15. according to the lubricating oil composition of claim 14, this lubricating oil composition is a lubricant peculiar to vessel.
16. according to the lubricating oil composition of claim 15, this lubricating oil composition is the plunger tpe marine engine oil.
17., also comprise oil fuel with irreducible oil content according to the lubricating oil composition of claim 14.
18. the lubricating method of plunger tpe marine diesel engine comprises to described engine providing according to each lubricating oil composition of claim 14 to 17.
19. according to each the purposes of washing agent in lubricating oil composition of claim 1 to 13, the bituminous matter component of its said composition that when being used for the plunger tpe marine diesel, is used to suspend.
CNB021047502A 2001-02-16 2002-02-10 High alkali cleaning additive Expired - Fee Related CN1314785C (en)

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ATE350435T1 (en) 2007-01-15
DE60217204D1 (en) 2007-02-15

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